Discoloration resistant fabric

ABSTRACT

A vinyl fabric includes a polymeric film supported on a substrate. The polymeric film is provided from a composition that includes one or more chlorinated resins (particularly PVC), at least one polymeric plasticizer, large amounts of TiO2, and at least one antioxidant. The combination of the plasticizer, titania and antioxidant provides the film, and in turn the fabric, with improved resistance to discoloration, particularly pink staining as results from the presence of chromophores produced by Streptoverticillium reticulum.

CROSS-REFERENCE TO RELATED APPLICATIONS

This international application claims the benefit of U.S. provisionalpatent application No. 62/629,380, filed on 12 Feb. 2018, incorporatedherein by reference in its entirety for all purposes.

BACKGROUND INFORMATION

PVC resin-based (vinyl) fabrics are used in a wide range of applicationsincluding, for example, as upholstery fabrics for restaurants, officesand marine vessels.

Vinyl fabrics typically include a PVC resin-containing layer supportedon a suitable substrate such as a natural or synthetic cloth. The PVCresin-containing layer can include one or more inorganic fillers, e.g.,TiO₂, CaCl₂, etc.

Products made from only PVC resins tend to be hard and sometimesbrittle. Plasticizers can blended with the resins to make resultingproducts more flexible and softer to the touch. Plasticizers for PVCresins can be small molecules, such as phthalates and terephthalates, orpolymers such as polyesters (including those made with adipic acid).

When used in wet, humid, or outdoor applications, vinyl fabrics can froma discoloration problem known as “pink staining” (although thediscoloration may be many colors other than or in addition to pink).Pink staining often is most obvious on light colored fabrics, inparticular different shades of white.

Pink staining is caused by the bacterium Streptoverticillium reticulum,which lives and grows in dark, wet conditions, such as those inside anupholstered item such as on the lower face of an upholstery fabric. Thebacteria generate chromophore(s) that cause the discoloration. Thediscoloration then migrates to the surface where it then becomesvisible. Once visible, the discoloration (stain) is notoriously hard toremove.

The marine industry has wrestled with pink staining for decades. It wasnoted as a problem at least as early as the 1980s, with significanteffort to avoid, ameliorate or correct the discoloration problem havingbeen extended ever since. One approach has been to employ a variety ofbiocides.

Arsenic has been used with some beneficial results, but arsenic ishighly toxic to humans and animals. It cannot be used in Europe and isbeing phased out elsewhere.

Other biocides have not been as effective as desired, with some workingonly for relatively short periods and others, unfortunately, not at all.

Pink staining remains an ongoing problem even today. Technical solutionsthat prevent or correct pink staining remain desirable.

SUMMARY

Provided herein are PVC resin-based compositions that can be formed intofabric components which help to protect those fabrics against surfacediscoloration caused by pink staining. The protection is long-lastingand effective. The strategies of the present invention also can protectsurfaces from other kinds of discoloration and problems that result frommigration to a fabric surface.

The present invention uses a protection strategy that may provideprotection according to two independent mechanisms: (1) an integralbarrier within the fabric that acts as a physical barrier to stopotherwise mobile chromophores from migrating from a lower region to thesurface where discoloration becomes visible and (2) avoidance oftransport mechanisms that allow the chromophores to be mobile in thefirst instance.

The aforedescribed protection results at least in part from the presencein the PVC resin-based composition of a discoloration inhibitingadditive package that includes at least or only three ingredients: apolymeric plasticizer, a larger-than-usual amount of TiO₂, and anantioxidant. In combination, these three ingredients are particularlyeffective at blocking chromophore migration and other staining agentsfrom transferring from one side of a fabric to the other.

In one aspect, the present invention relates to a fabric which includesa substrate and, provided thereon, a polymeric film. The latter includesat least one chlorinated resin, a plasticizing amount (i.e., effectiveamount) of a polymeric plasticizer, 10 to 30 phr TiO₂, and 0.1 to 10 phrantioxidant.

In another aspect is provided an upholstery cushion that includes theaforedescribed fabric covering at least a portion of a three-dimensionalcore.

In a related aspect is provided the foregoing upholstery cushion havingin its interior Streptoverticillium reticulum bacteria andchromophore(s) produced thereby, but the outer surface of the fabriccomponent is substantially free of discoloration caused by the presenceof those chromophore(s).

In yet another aspect is provided a marine vessel which includes atleast one of the aforedescribed fabric and upholstery cushion.

Also provided are methods of making the fabric, upholstery cushion, andmarine vessel.

Other aspects of the invention will be apparent to the ordinarilyskilled artisan from the detailed description that follows. To assist inunderstanding that description, certain definitions are providedimmediately below, and these are intended to apply throughout unless thesurrounding text explicitly indicates a contrary intention:

-   -   “resin” or “polymer” means the polymerization product of one or        more types of monomers and is inclusive of homo-, co-, ter-,        tetra-polymers, etc.;    -   “interpolymer” means a polymer that includes mer units derived        from at least two reactants, typically monomers, and is        inclusive of copolymers, terpolymers, tetra-polymers, and the        like;    -   “mer” or “mer unit” means that portion of a polymer derived from        a single reactant molecule (e.g., ethylene mer has the general        formula —CH₂CH₂—);    -   “phthalate” means a salt and/or ester of phthalic acid;    -   “terephthalate” means a salt and/or ester of terephthalic acid;    -   “(meth)acrylic” means acrylic or methacrylic;    -   “pbw” means parts by weight;    -   “phr” (parts per hundred parts resin) means pbw per 100 pbw        resin; and    -   “substantially free”    -   in connection with small molecule plasticizers in a polymeric        film, means less than 0.1, preferably less than 0.05, phr, and    -   in connection with discoloration, means no noticeable        discoloration when viewed under ambient room lighting.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a marine vessel which includes a fabric of the presentinvention.

FIG. 2 schematically shows a cross-section of an upholstery cushionincorporating the fabric of the present invention.

FIG. 3 schematically shows a cross-section of the fabric component ofthe upholstery cushion from FIG. 2.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The embodiments described below are not intended to be exhaustive or tolimit the invention to the precise forms disclosed. Instead, theembodiments are chosen and described so that those skilled in the artmay appreciate and understand the principles and practices of thepresent invention.

The present invention provides PVC resin-based fabrics that are usefulin a wide range of applications, non-liming examples of which includefabric coverings for seating, cushions, pillows, luggage, bags,backpacks, clothing, headgear, wallcoverings, and window treatments.Many embodiments of the fabrics of the present invention are weatherresistant and waterproof and thus are useful as upholstery fabric inmarine applications such as marine cushions and the like.

FIG. 1 depicts a marine vessel 10 including an upholstery cushion 12that is covered at least in part by a fabric 14 of the presentinvention.

As seen in FIG. 2, upholstery cushion 12 includes a three dimensionalcore 16. Fabric 14, which includes an outer surface 30, covers at leasta portion of core 16. Fabric 14 may be affixed to the core 16 using anysuitable attachment method(s) including, but not limited to, adhesive ortape, stitching, staples, rivets, snaps, other fasteners, clips, clamps,drawstrings, and combinations of these.

Core 16 often includes a foam body 18 that is resiliently compressibleby a user. Cushion 12 optionally can include a rigid backer 20 to helpprovide structural support when cushion 12 is used as a seat or has anadditional function as a lid for a storage compartment or the like.Rigid backers may be made from a wide range of natural and/or syntheticmaterials such as wood, composite panels such as plywood, polymericpanels, metal plates, etc.

Fabric 14 generally includes substrate 22 and, provided thereon, apolymeric film 24. Substrate 22 serves as a structural backing andreinforcement for fabric 14. Substrate 22 desirably is flexible andpossesses sufficient elasticity for the particular end-use application.Where fabric 14 might be exposed to water, high humidity, or othermoisture, substrate 22 desirably is hydrophobic, water resistant, and/orwaterproof to minimize absorption or other undesirable, water-associatedeffects.

A wide variety of materials are suitable to form substrate 22. Suitableexamples include a wide variety of film-based, woven, or non-wovencloths made from any suitable natural or synthetic material. Woven ornonwoven synthetic cloths are particularly useful when fabric 14 is tobe used in marine environments. In one embodiment, a polyester clothknitted with a circular weave and having a weight of 3 oz./yd.² wasfound to be suitable. This cloth may be treated using conventionalstrategies to improve adhesion of polymeric film 24 to the cloth.Substrate material including filament fibers may be used as analternative or in combination with spun fibers, but filament fibers havea tendency to provide stiffer fabric embodiments.

The cloth may be treated to help promote adhesion of polymeric film 24to the cloth. A wide variety of such treatments may be used singly or incombination such etching, exposing to ultraviolet light, exposure to anelectron beam, priming with a suitable primer or adhesive, chemicallymodifying the surface, combinations of these, or the like.

Pink staining tends to originate proximal to substrate 22 because thisis where Streptoverticillium reticulum bacteria typically live andgenerate chromophore(s) that cause the discoloration. The presentinvention advantageously provides an extremely effective way to preventthis discoloration from reaching outer surface 30 of fabric 14. Theprotection is long-lasting, not consumed by its protective function (aswould be true with many biocides), and is integral with fabric 14. Theresult is that the protection remains in place as fabric 14 is used.

Polymeric film 24 can be formed from a single, layer or may be alaminate of two or more layers that are individually formed.Alternatively, polymeric layer can be formed from multiple layers formedin situ. As shown in FIG. 3, polymeric film 24 has a multi-layerstructure in which multiple layers are formed in situ duringmanufacture, described further below.

Polymeric film 24 includes a foamed lower layer 26 and an outer skinlayer 28. Setting aside the foamed structure of lower layer 26, thecomposition of lower layer 26 and outer skin layer 28 may be the same ordifferent.

Foamed lower layer 26 has a lower surface 25 adhered to substrate 22 andan upper surface 27 integrally formed to outer skin layer 28.

Outer skin layer 28 has lower surface 29 integrally formed to lowerlayer 26 and outer surface 30 generally visible to the user. (Outersurface 30 also is the surface 30 of fabric 14 that a user feels ortouches.) As an option, outer surface 30 may include features to providea desired texture or pattern. Embossing often is a suitable technique toform such a texture or pattern.

Polymeric film 24 includes at least one chlorinated resin deployed inlayers 26 and/or 28, preferably both layers 26 and 28. Chlorinatedresins help to provide fabric 14 with excellent hand, visual appearance,and durability, particularly in marine environments in which fabric 14is exposed to solvents, fresh water, salt water, and the like.

Useful resins include at least 10, preferably at least 20, or morepreferably at least 50 mer units and up to 100, 500, 1000, or 5000 merunits. The weight average molecular weight (M_(w)) can range from 500 to200,000, preferably 1000 to 150,000, more preferably 2000 to 100,000g/mol.

A chlorinated resin refers to a resin derived from one or morereactants, at least one of which is at least includes at least one Clatom. Optionally, such reactants may be per-chlorinated (i.e., all Hatoms replaced by Cl atoms). The Cl substituents of the chlorinatedreactant(s) may be attached directly to the reactant backbone by asingle bond or via a suitable linking group. In some embodiments,chlorinated reactants may be monomeric, oligomeric, and/or polymeric.

The Cl content of the chlorinated resin can vary over a wide range. Inmany embodiments, it is desirable that a chlorinated resin includes atleast ˜20%, preferably at least ˜40%, and more preferably at least ˜60%Cl (all w/w). Perchlorinated embodiments represent a practical upperlimit upon Cl content.

Desirably, such chlorinated reactants are free radically polymerizable.Free radical polymerization can occur via a variety of techniquesincluding suspension polymerization, bulk polymerization, emulsionpolymerization or solution polymerization.

Examples of free radically polymerizable functionalities includeolefinic C—C double bonds, (meth)acrylic groups, allyloxy groups, vinylgroups (e.g., styrenic compunds), cyanate ester groups, vinyl acetate,vinyl ether groups, combinations of these, and the like. Free radicallypolymerizable functionality is conveniently reacted by exposing thereactants to a suitable source of curing energy, often in the presenceof agents (e.g., initiators, etc.) that help promote the desiredreaction. The energy source used for achieving polymerization and/orcrosslinking of the curable functionality may be actinic (e.g.,radiation having a wavelength in the UV or visible region of thespectrum), accelerated particles (e.g., e-beam radiation), thermal(e.g., heat or infrared radiation), or the like.

Illustrative embodiments of free radically polymerizable, chlorinatedreactants useful for making chlorinated resins may have structuresincluding 2 to 20, preferably 2 to 10, more preferably 2 to 4 C atomsand at least one C—C double bond. More preferred are partially or fullychlorinated ethenes, chlorinated propenes, and combinations of these,such as monochloroethene (vinyl chloride monomer), 1,2-dichloroethene,1,1,2-trichloroethene, tetrachloroethene, 1-chloropropene,2-chloropropene, 1,1-dichloropropene, 2,2-dichloropropene,1,2-dichloropropene, 1,1,1-trichloro-2-propene, 1,1,2-1-propene,1,2,3-trichloropropene, combinations of these, and the like.

A preferred class of chlorinated resin is polyvinyl chloride, alsoreferred to herein as PVC polymers or resins. A PVC resin refers to ahomo- or interpolymer that includes mer resulting from incorporation ofvinyl chloride monomer, CH₂=CHCl. PVC resins which include at least 50%,preferably at least 90%, more preferably at least 99%, and mostpreferably substantially 100% (all w/w) vinyl chloride mer arepreferred. A PVC resin formed from only vinyl chloride monomer (exceptfor terminal end groups) is thermoplastic, linear, and very strong.

The PVC resin(s) may be thermoplastic or thermosetting. ThermoplasticPVC resins are preferred for use in the illustrative manufacturingmethod described below.

Different PVC resins and methods of making PVC resins are widelydescribed in the patent and technical literature; see, e.g., U.S. Pat.Nos. 4,418,169 and 5,290,890; U.S. Pat. Publ. Nos. 2012/0095176 and2012/0177856. PVC resins are commercially available from a variety ofcommercial sources. Examples include SG710 resin suspension (ThaiPlastic and Chemicals Public Co., Ltd.; Thailand); Formosa F676 andF2110 resins (Formosa Plastics Corp.; Livingston, N.J.); Oxy ChemOxyvinyl 500F (OxyVinyls, LP; Dallas, Tex.); and Shintech SE1300F(Shintech, Inc.; Houston, Tex.).

Polymeric film 24 also includes at least one polymeric plasticizer thatis used in an amount effective to improve the flexibility of thepolymeric film 24 and corresponding fabric 14. A polymeric plasticizeralso may help to provide a softer feel to fabric 14.

As used herein, a plasticizer refers to a compound that increases theflexibility of chlorinated resins, particularly PVC, and a polymericplasticizer refers to a polymer capable of acting as a plasticizer.

In many embodiments, a suitable polymeric plasticizer meets twocriteria: (1) full miscibility with the chlorinated resin(s) (with fullymiscibility considered to be the presence of a single phase at 25° C. ina 20 phr composition) and (2) a glass transition temperature (T_(g))that is lower than the T_(g) of any of the chlorinated resin(s) in thecomposition (with T_(g) being determinable via DSC). Generally, theplasticizer T_(g) desirably is at least 10°, preferably at least 20°,and more preferably at least 30° C. lower than that of the resin(s) inthe composition.

The polymeric plasticizer can have M_(w)≥1000, preferably ≥2000, or morepreferably ≥3000. The molecular weight can be limited to make it easierto blend or otherwise use the plasticizer to make fabric 14; forexample, polymeric plasticizer can have M_(w)≤150,000, preferably≤100,000, or more preferably ≤75,000. (Molecular weight ranges can beprovided by combining any of the lower limits with any of the upperlimits.)

One class of polymers suitable for use as plasticizers for PVC includesadipic acid polyester polymers. A wide variety of polymeric plasticizersavailable from many commercial sources, non-limiting examples of whichinclude ELVALOY HP plasticizers (Dow DuPont; Wilmington, Del.); ADMEXplasticizers Eastman Chemical Company (Kingsport, Tenn.); PALAMOLLplasticizers BASF (Leverkusen, Germany); and the PN series ofplasticizers (Adeka; Tokyo, Japan).

The amount of polymeric plasticizer(s) present in polymeric film 24 iseffective to help plasticize the PVC resin(s). A wide range of amountswould be suitable depending on the degree of flexibility and softnessdesired. As illustrative guidelines, the weight ratio (on a solidsbasis, exclusive of solvent) of chlorinated resin(s) to polymericplasticizer(s) can range from 1:10 to 10:1, preferably from 1:5 to 5:1,more preferably from 1:2 to 2:1, even more preferably from 3:4 to 4:3,and most 1:1±10%.

Significantly, use of a polymeric plasticizer is one of the features ofthe present invention that works in combination with other componentsdescribed herein to help prevent surface discoloration of the fabric 14associated with Streptoverticillium reticulum.

The polymeric plasticizer may help prevent discoloration by one or morepossible mechanisms. First, a polymeric plasticizer may be more fixedand less mobile in the resultant film as compared to small moleculeplasticizers such as a phthalate; in combination with a high loading ofTiO₂ and an antioxidant, this immobility appears to help establish abarrier that blocks internal discoloration from reaching outer surface30 of fabric 14.

Second, and related to the first, the reduced mobility of a polymericplasticizer might reduce the rate of transport of chromophores producedby Streptoverticillium reticulum bacteria from the interior of theupholstery, where the bacteria thrive, to outer surface 30; this is incontrast to the significant mobility of small molecule plasticizers.

Third, the high loading of TiO₂ and antioxidant(s) are believed tocontribute to the relative immobility of the polymeric plasticizer.

Thus, it is believed that all three components—polymeric plasticizer,the high loading of TiO₂, and antioxidant—cooperate to help establish amore effective discoloration barrier and/or to more effectively deny thediscoloration a transport mechanism to reach outer surface 30. Incertain embodiments, the three ingredients alone (or with minor amountsof other ingredients) constitute a discoloration inhibiting additivepackage.

The presence of small molecule plasticizers such as phthalates orterephthalates can worsen discoloration problems associated withStreptoverticillium reticulum in upholstery fabric 14. However, thecombination of the polymeric plasticizer, high loading of TiO₂, andantioxidant(s) can help alleviate discoloration even if certain smallmolecule plasticizers, particularly phthalates or terephthalates, arepresent, although the best protection against discoloration is achievedif small molecule plasticizers (having a molecular weight under about750 g/mol, or even under about 500 g/mol) are omitted. Accordingly,polymeric film 24 of the present invention desirably is substantiallyfree of phthalate and/or terephthalates small molecules and/or otherplasticizer small molecules

Polymeric plasticizer may be uniformly distributed throughout polymericfilm 24 such that the composition of polymeric film 24 with respect tothe plasticizer is uniform throughout both foamed lower layer 26 andouter skin layer 28.

Alternatively, the polymeric plasticizer may be deployed selectivelyonly in portions of polymeric film 24. For example, in one embodiment,the polymeric plasticizer is selectively incorporated into foamed lowerlayer 26. In this way, the plasticizer is able to function as a barrierand to block discoloration transport in the region of polymeric film 24most proximal to the Streptoverticillium reticulum causing thediscoloration. This selective incorporation avoids using the plasticizerin the outer skin layer 28, which is advantageous because a polymericplasticizer is a relatively expensive ingredient. If polymericplasticizer is selectively incorporated into only one or more portionsof polymeric film 24, the weight ratio of the plasticizer used is stillbased on the total amount of PVC resin(s) used throughout polymeric film24.

The polymeric film 24 further includes TiO₂. When used at relativelyhigh loadings and in combination with the polymeric plasticizer(s) andthe antioxidant, TiO₂ helps to prevent surface discoloration on fabric14. The TiO₂ is believed to help both establish a barrier to blockdiscoloration as well as interrupt transport mechanisms that wouldotherwise shuttle discoloring chromophores from their bacterial sourceto the surface.

Any form of titania, including monoclinic, rutile, anatase, andbrookite, can be used. A rutile embodiment presently is preferred.

The TiO₂ particles may have diameters within a wide range. As generalguidelines, the TiO₂ particles can have an average diameters in therange from 0.05 to 1.0 μm, preferably 0.1 to 0.5 μm, more preferably 0.1to 0.3 μm. In one experiment, an average particle size of 0.2 μm wasfound to be suitable. (Average particle size may be determined accordingto ISO 13317-3:2001.)

Polymeric film 24 incorporates TiO₂ at a weight loading that is higherthan is typical in most vinyl upholstery fabrics. As general guidelines,polymeric film 24 includes from ˜7 to ˜30, preferably from ˜10 to ˜30,phr TiO₂.

Polymeric film 24 also includes one or more antioxidants, which aremolecules that inhibit the oxidation of other molecules. Use of anantioxidant with chlorinated resins in upholstery fabric applicationsbecause because resins generally are considered to be highly resistantto oxidation. However, antioxidants appear to provide additionalfunctionality in polymeric film 24. When used in combination with thepolymeric plasticizer(s) and TiO₂, the antioxidant(s) help to preventsurface discoloration of fabric 14.

A wide variety of antioxidant(s) may be used in polymeric film 24. Apreferred class of antioxidants is the sterically hindered, hydroxylfunctional, aromatic antioxidants. Such antioxidants include at leastone hydroxyl group pendant directly or indirectly from an aromaticmoiety, wherein at least one, preferably two, substituents are ortho tothe pendant hydroxyl group. A phenyl moiety comprising at least onelinear or branched C₁-C₁₀ alkyl group ortho to the OH group of thephenol are preferred. More preferred alkyl moieties include methyl,ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, and the like.

Preferred antioxidants are those having molecular weights of from 500 to5000 g/mol. Such higher molecular weight antioxidants preferably arebranched compounds that include a plurality (e.g., 2-10, often 2-6) ofsterically hindered phenol moieties independently attached to a commoncarbon atom by a single bond or a divalent linking group having up to 5,10 or even 20 C atoms. In some embodiments, the linking groups may bepart of a common ring structure with each other and/or the common carbonatom. Additionally or alternatively, the divalent linking group caninclude one or more ester linkages.

An illustrative example of a branched compound that includes multiplesterically hindered phenol moieties has the following formula (with“tBu” representing a t-butyl group):

The amount of antioxidant(s) used in polymeric film 24 may be selectedwithin a wide range, for example, from 0.1 to 10, preferably 0.5 to 5,phr antioxidant. If too little is used, the ability of the antioxidantto help protect against discoloration may be less than desired. Usingtoo much may be wasteful in the sense of providing little extraprotection while potentially risking a reduction in desired performancecharacteristics.

As an option, polymeric film 24 may include one or more additionalingredients to facilitate manufacture of fabric 14, to help adjustproperties of fabric 14, or the like. By way of example, optionalingredients may include one or more of UV stabilizers, coloring aids,lubricants (such as to help prevent sticking of the fabric components toequipment during manufacture and/or to prevent blocking of finishedfabric 14), biocides, antistatic agents, inorganic fillers (other thantitania), blowing agents (which can be incorporated into a portion of apolymer film precursor during manufacture such as foamed lower layer26), antifoaming agents (whcih can be included in other portions such asouter skin layer 28), authentication taggants, other polymers, and thelike.

Fabric 14 can be provided in a variety of ways.

A composition that is a precursor of the foamed lower layer 26 (firstprecursor composition) is applied onto substrate 22. The first precursorcomposition generally includes a chlorinated resin (e.g., PVC), apolymer plasticizer, TiO₂, and an antioxidant as described above. Thefirst precursor composition also may include a blowing agent to helpprovide the foam structure of lower layer 26, one or more suitablesolvents, and/or processing aids to help reduce the tendency of theapplied precursor coating to stick to fabrication equipment such assteel rolls on calendaring equipment. An exemplary first precursorcomposition is provided in Table 1, immediately below.

TABLE 1 Exemplary first precursor composition Amount Ingredient (pbw)SG710 PVC resin suspension 100.00* ADK CIZER PN-310 adipic acidpolyester polymeric plasticizer 92.00* UV and thermal stabilizers 2.24CaCO₃ filler 20.00 blowing agent 3.94 foam cell adjuster for fine foam2.5 powder lubricants 5.42 TiO₂, rutile 9.00 antioxidant containing foursterically hindered phenol moieties 2.00 Biocide 5.00 *Includes solventas supplied by commercial source.

The first precursor composition is cured. Only partial foaming, if any,is allowed to occur at this stage by curing the first precursor layer ata sufficiently low temperature to avoid unduly activating the blowingagent.

Thereafter, a second precursor composition, from which outer skin layer28 will be formed, is applied on lower layer 26. The second precursorcomposition generally is similar to the first except that the secondneed not include blowing agents or associated additives if outer skinlayer 28 is not desired to be in the form of a foam. The secondprecursor composition optionally may include one or more colorants toadjust the color of outer skin layer 28 which, unlike lower layer 26, isvisible to the end user. For example, the TiO₂ tends to provide a verystark white color to fabric 14, although small amounts of colorants tosoften the white (to ivory, eggshell, beige or other more muted colors)or to provide other hues may be used. An exemplary second precursorcomposition is provided in Table 2, immediately below.

TABLE 2 Exemplary second precursor composition Amount Ingredient (pbw)SG710 PVC resin suspension 100.00* ADK CIZER PN-310 adipic acidpolyester polymeric plasticizer 96.00* UV and thermal stabilizers 2.50CaCO₃ filler 25.00 powder lubricants 4.25 TiO₂, rutile 25.00 antioxidantcontaining four sterically hindered phenol moieties 2.00 colorants 0.14biocide 5.30 *Includes solvent as supplied by commercial source.

The second precursor composition then is cured before the entirestructure is heated in a foaming oven to activate the blowing agent inthe first precursor layer, which causes the first precursor compositionto foam and expand, providing an expanded layer (e.g., 55 to 60 milsthickness). If desired, the product can be compressed to a desired finalthickness such as, e.g., 40 mils.

The compression may occur with embossing to help provide a desiredtexture or pattern on the surface.

PVC films have a tendency to be naturally tacky and may have low surfacetension. Accordingly, a suitable top finish may be applied onto outerskin layer 28 to provide a desired finish, to seal the surface, and toreduce tackiness. A suitable top finish may be applied at any desiredcoating weight such as from 7 to 8 g/m². For a review of coating andlamination techniques used with fabrics, the interested reader isdirected to K. Singha, “A Review on Coating & Lamination in Textiles:Processes and Applications,” Am. J. Poly. Sci., 2012, 2(3): 39-49.

While various embodiments of the present invention have been provided,they are presented by way of example and not limitation. To the extentfeasible, as long as they are not interfering or incompatible, featuresand embodiments described above in isolation can be combined with otherfeatures and embodiments.

The relevant portions of any document specifically referenced in thepreceding text or in the examples that follow are incorporated herein byreference.

The following non-limiting, illustrative examples provide the readerwith detailed conditions and materials that can be useful in thepractice of the present invention.

EXAMPLES Example 1 permanent Marker Test

A study was conducted to evaluate the ability different plasticizers tohelp PVC-based fabric resist discoloration due to chromophores provduedby Streptoverticillium reticulum.

A control sample was prepared from a formulation including 100 pbw PVCresin, 88 pbw diisononyl phthalate (DINP) as a monomeric plasticizer,and 27.5 pbw TiO₂.

A first embodiment of a PVC resin composition of the present inventionwas prepared similarly except that 94 pbw adipic acid polyester was usedas plasticizer in place of DINP, the amount of TiO₂ was increased to 34pbw, and 1.6 pbw antioxidant with four sterically hindered phenolmoieties was included.

A second inventive composition was prepared in an identical mannerexcept that a different type of TiO₂ was used.

Using black, blue, and red permanent markers, color stripes were appliedto the front side of each of the samples.

The marked samples were held for 2 hours in an oven set at 180° F.

Upon removal, the samples were examined for color transfer to the backside. The control sample showed a high degree of color transfer throughthe sample; all three colors were easily visible from the back side. Nocolor transfer was visible with respect to the other two samples.

Example 2 bacterial Chromophore Testing

ASTM 1428—15 a describes a test titled “Standard Test Method forEvaluating the Performance of Antimicrobials in or on Polymeric SolidsAgainst Staining by Streptomyce species (A Pink Stain Organism),”designed to determine the effectiveness of antimicrobials in vinylfabrics.

Using the same formulations provided above in Example 1, additionalsamples were prepared to evaluate resistance to discoloration resultingfrom Streptoverticillium reticulum-origin chromophores.

While commercial embodiments of the finished product are expected toinclude one or antimicrobial(s) so as to inhibit microbial growth,samples without any antimicrobials were prepared to determine theability to prevent staining. (Pink staining often occurs even whenantimicrobials are present, which further reflects the need for asolution to the staining issue.)

The bacterium was inoculated onto an agar surface with a nutrient richgrowth medium using the parallel streak method.

Each sample was marked on one side with an ink pen identifier, with thatsame area then being coated with a portion of the bacterial challengematerial. Each sample was exposed to the organism for 14 days, afterwhich each sample was evaluated for color transfer of the discoloringchromophore(s). Discoloration was observed on all the samples on theside coated with challenge material, which confirms production of of thediscoloring chromophore(s).

Resistance to color transfer from the agar side to the other side wasquite different for the samples, however.

Both the ink pen and the chromophore-induced discoloration transferredthrough the control sample and were readily observable on the oppositeside.

For the two inventive samples, however, no color transfer of thediscoloration or the ink pen was seen.

1. A fabric, comprising: a) a substrate; and b) provided on saidsubstrate, a polymeric film that comprises 1) at least one chlorinatedresin, 2) an effective amount of a polymeric plasticizer, 3) 10 to 30 atleast 10 phr TiO₂, and 4) 0.1 to 10 phr antioxidant.
 2. The fabric ofclaim 1, wherein the polymeric plasticizer, the TiO₂, and theantioxidant are constituents of a discoloration inhibiting additivepackage, and wherein the discoloration inhibiting additive packageconsists essentially of the polymeric plasticizer, the TiO₂, and theantioxidant.
 3. An upholstery cushion, comprising a) a three-dimensionalcore; and b) a fabric that comprises 1) a substrate and 2) provided onsaid substrate, a polymeric film that comprises (A) at least onechlorinated resin, (B) an effective amount of a polymeric plasticizer,(C) 10 to 30 phr TiO₂, and (D) 0.1 to 10 phr antioxidant.
 4. Theupholstery cushion of claim 3 further comprising discoloration resultingfrom at least one chromophore produced by the Streptoverticilliumreticulum bacteria in the interior of said cushion, wherein an outersurface of said upholstery cushion is substantially free of saiddiscoloration.
 5. The upholstery cushion of claim 3, wherein thepolymeric plasticizer, the TiO₂, and the antioxidant are constituents ofa discoloration inhibiting additive package, and wherein thediscoloration inhibiting additive package consists essentially of thepolymeric plasticizer, the TiO₂, and the antioxidant.
 6. The upholsterycushion of claim 5 further comprising discoloration resulting from atleast one chromophore produced by the Streptoverticillium reticulumbacteria in the interior of said cushion, wherein an outer surface ofsaid upholstery cushion is substantially free of said discoloration. 7.The fabric of claim 1 wherein the at least one chlorinated resincomprises at least one polymer that comprises vinyl chloride mer.
 8. Thefabric of claim 7 wherein the polyvinyl chloride resin is thermoplastic.9. The fabric of claim 1 wherein said polymeric film comprises first andsecond film layers, said first film layer contacting said substrate andsaid second film layer overlaying said first film layer, wherein each ofsaid first and second film layers comprise a chlorinated resin, TiO₂,and an antioxidant and wherein at least said first film layer furthercomprises a polymeric plasticizer.
 10. The fabric of claim 1 whereinsaid polymeric plasticizer has a weight average molecular weight of from3000 to 75,000 g/mol.
 11. The fabric of claim 1 wherein said polymericplasticizer has a glass transition temperature that is at least 30° C.lower than the glass transition temperature of each of said at least onechlorinated resin.
 12. The fabric of claim 1 wherein the polymericplasticizer comprises or is an adipic acid polyester.
 13. The fabric ofclaim 1 wherein said polymeric film is substantially free of phthalatesand terephthalates.
 14. The fabric of claim 1 wherein said polymericfilm comprises a foamed lower layer and an outer skin layer, saidpolymeric plasticizer optionally being selectively deployed in saidlower layer.
 15. The fabric of claim 1 wherein said antioxidant has amolecular weight of from 500 to 5000 g/mol.
 16. The fabric of claim 15wherein said antioxidant comprises or is a sterically hindered phenol.17. The fabric of claim 16 wherein the sterically hindered phenol hasthe formula

where tBu represents a t-butyl group.
 18. The fabric of claim 1 whereinfrom 0.5 to 5 phr antioxidant is present in said film.
 19. A method ofmaking a fabric, said method comprising foil ling on a substrate apolymeric film from a composition that comprises at least onechlorinated resin, a polymeric plasticizer, at least 10 phr TiO₂ and atleast 0.1 phr antioxidant.
 20. The method of claim 19 wherein thepolymeric film formation involves sequential formation of first andsecond film layers, said first layer contacting said substrate and beingprovided from a first precursor composition to form a first polymericfilm layer on the substrate said second layer overlaying said firstlayer and being provided from a second precursor composition, whereineach of said first and second precursor compositions comprises at leastone chlorinated resin, TiO₂, and an antioxidant and wherein at leastsaid first precursor composition further comprises a polymericplasticizer.
 21. The method of claim 20 wherein said first precursorcomposition further comprises a blowing agent, said method furthercomprising heating said first and second layers in a manner effective tofoam and expand the first polymeric film layer.